Novel composition

ABSTRACT

NOVEL AMINO CYCLOPENTANE COMPOUNDS OF FORMULA A, PREPARED FROM A CYCLOPENTANE-1,3-DIONE, USEFUL FOR THE CONTROL OF INSECTS   1-(R1-C(-R)=CH-CH2-),1-R2,2-(R4-N(-R5)-),5-R6,5-OH-CYCLO-   PENTANE   WHEREIN EACH OF R, R1, R3, R4, AND R5 IS HYDROGEN OR LOWER ALKYL, R AND R1 TOGETHER FROM A CYCLOALKYL RING, AND R2 IS METHYL OR ETHYL.

United States Patent Oflice Patented May 8, 1973 ABSTRACT OF THE DISCLOSURE Novel amino cyclopentane compounds of Formula A, prepared from a cyclopentane-1,3-dione, useful for the control of insects R R R3 OK wherein each of R, R R R and R is hydrogen or lower alkyl, R and R together form a cycloalkyl ring, and R is methyl or ethyl.

This invention relates to novel compounds and the prep aration and use of the compounds. More particularly, the novel compounds of the present invention are represented by the following Formula A:

O R l R/Cp n R4 RI 0 \N/ ll R. L If R 521 11 R/\R 521 12 (III) IV In the practice of the above outlined syntheses, 2-methyl or 2-ethylcyclopentane-1,3-dione is reacted with an allylic alcohol of the Formula IA in the presence of an acidic catalyst to form the 2,2-disubstituted cyclopentanel,3- dione of Formula II R (IA) This reaction is performed neat or in an organic solvent inert to the reaction such as a hydrocarbon solvent under anhydrous conditions, and at a temperature above room temperature such as about 75 C. to 150 C. The reaction of a diketone of Formula II with a reducing agent such as lithium aluminum tri-t-butoxy hydride, lithium aluminum tri-methoxy hydride and the like in organic solvent inert to the reaction such as an ether solvent affords a compound of Formula III wherein R is hydrogen as a mixture of the alpha and beta hydroxy compounds. To form a compound of Formula III wherein R is lower alkyl, a diketone of Formula II is reacted with a Grignard R MgX wherein X is bromo or chloro or a alkyl lithium of the formula R Li. The product is obtained as a mixture of isomers which can be separated by chromatography or distillation if desired. A'ketol of Formula III is converted into a secondary or tertiary amino compound of Formula IV by reaction of the ketol with the appropriate primary or secondary amine in the presence of sodium cyanoborohydried in absolute methanol buffered to about pH 5. Primary amines of Formula IV are prepared by the reaction of the ketol compound III with ammonia in absolute methanol in the presence of lithium cyanohydridoborate. This method can be used also for preparation of secondary and tertiary amines of Formula IV. Borch and Durst, J. Am. Chem. 'Soc. 91, 39 96 (1969).

The compounds of Formula A are useful for the control of insects. Without any intention of being bound by theory, it is believed that the effectiveness of these compounds is attributable to their capability of inhibiting moulting hormone biosynthesis and thereby prevent development of immature insects and prevent essential processes in adults which require moulting hormone for normal development. Delivery of the compounds into the active site Within the insectcan be accomplished bytopical application or by ingestion, treatment of the insects food. Generally, a dosage within the range of about one to twentyfive micrograms per insect is used. Typical insects include Lepidoptera, Diptera, Coleoptera and Orthoptera. The compounds of Formula A are useful as anti-bacterial and anti-fungal agents also such as members of Carynebacterium, Erwinia, Xanthomonas, Pseudomonas, Agrobacterium, Rhizobium, Fusarium and Alternan'a. The compounds of Formula A are useful also as hardening agents and accelerators for the hardening of liquid epoxy resins for casting.

The wavy line (2) in the formulas herein indicates alpha and beta isomerism.

The following examples are provided to illustrate the present invention.

EXAMPLE 1 A mixture of 11.2 g. of Z-methylcyclopentane-1,3-dione, 29 g. of allyl alcohol, 100 mg. of para-toluene sulfonic acid and about 2 g. of anhydrous calcium sulfate in a glass bomb is heated in an oil bath at for about 15 hours. The mixture is then poured into water and thoroughly extracted with'ether. The ether phase is washed with water and brine, dried over calcium sulfate and concentrated.

The concentrate is distilled to yield 2-allyl-2-methyleyclopentaneJfi-dione. (cf- Crispinet al.-, J. Chem. 'Soc. C, 1970, 10).

EXAMPLE 2 To a mixture of 1.52 g. of 2-allyl-2-methylcyclopentane-. 1,3-dione and 80 ml. of dry tetrahydrofuran, under nitrogen and at is added 2.79 g. of lithium aluminum tri-tbutoxy hydride in 100 ml. of tetrahydrofuran slowly. The

reaction mixture is stirred at 25 for 16 hours. Then tube is heated 2.5 hours at 130. The mixture is dissolved in ether, washed with cold 2 N sodium hydroxide, water and brine, dried over calcium sulfate and solvent removed to yield crude 2-(3'-methylbut-2-enyl)-2-methylcyclopentane-1,3-dione which can be purified by fractional distillation.

EXAMPLE 4 V To-:a mixture of 2.7 g. of 2-(3'-methylbut2'-enyl)-2- methylcyclopentane-l,3-dione'in 80 ml. of dry tetrahydrofuran, under nitrogen and at 0, is added 4.2 g. of lithium aluminum tri-t-butoxy hydride in '100. ml. of dry tetrahydrofuran. The reaction mixture is stirred. at 25 for V 18 hours and then 140 ml. of saturated sodium sulfate is added. The mixture is filtered directly into a separatory funnel and residue salts washed with ether. The ether phase is washed with brine, dried over calcium sulfate and evaporated to give 3-hydroxy-2-(3'-methylbut-2- enyl)-2-methylcyclopentan-l-one (predominantly. 3u5hy- .droxy) whichcan be purified by fractional distillation.

EXAMPLE 5 To a mixture of 756 mg. of isohexylamine, 30 ml. of anhydrous methanol, and 283 mg. of sodium cyanoborohydride, under nitrogen, adjusted to pH 5 by addition of dry hydrogen chloride,"is added 231 mg. of 3-hydroxye2- pound, i.e.,

I 3-hydroxy-2- 3 '-methylpent-2'-enyl -2 -methylcyclopentan-l-one, and t 3 -hydroxy-2- 3 -ethylpent-2-eny1) -2-methylcyclopentanl-one, respectively.

Following the procedure of Example 5, each of the thus-prepared S-hydroxy-l-keto compounds is reacted with isohexylamine to produce the respective amino corn- 1- (N-isohexylarnino) -3-hydroxy-2- (n-but-2-euyl -2- (nbut-2"-enyl )-2-methylcyclopentane,.

1- N-isohexylamino) -3- hydroxy-2- (n-pent-2'-enyl) -2- methylcyclopentane, Y

' 1- (N-isohexylarnino) -3 -hydroxy-2- (3 methylpent-2'.-

enyl)-2-methylcyclopentane and 1- (N-isohexyl amino -3-hydroxy-2- 3 -ethylpent-2- enyl)-2-methylcyclopentane, respectively.

EXAMPLE 7 Six ml. of a 3 M solution of methylmagnesium bromide in ether is added slowly to2.5 .g. of 2-allyl-2-methylcyclopentane-1,3-dione in 25 m1.fof dry ether. After addition is complete, the mixture is heated'at reflux for one hour,

cooled to 0 and then treated with saturated aqueous am- 7 monium chloride until the reaction subsides. The organic layer is separated, combined with ether extracts of aqueous layer, and washed with water and brine. After drying over magnesium sulfate, solvent is evaporated to yield 3-hydroxy-3 -methyl-2-allyl-2-methylcyclopentan-1- one which is purified by chromatography.

7 Following the process of. Example 5, l-(N-is'ohexylamino)-3-hydroxy-3 methyl-2-allyl 2 methylcyclopentane is prepared from the product of this example.

EXAMPLE 8 Following the procedure of'Example 5 each of isopentylamine, methyl n-butylamine, methyl isopentylamine, methyl isobutyl amine and methyl isohexylamine is reacted with 3-hydroxy-2 -(3'-methylbut-2-enyl)-2- methylcyclopentan-l-one to prepare 3-hydroxy-2-(3'-methylbut-2' enyl)-2- methyl-l-(N-isopentylamino) cyclopentane,

allyl-2-methylcyclopentan-l-one. After about 48 hours,

the mixture is poured into cold 5% sodium bicarbonate solution and then extracted with ether. The ethereal extract is washed, dried and evaporated under reduced pressure to yield 3-hydroxy-2-allyl-2-methyl-l-(N-iso hexylamino) cyclopentane.

By repeating the process of this example with the exception of using 3-hydroxy-2-(3-methylbut-2'-enyl)-2- methylcyclo-l-one as the ketone starting material, there is produced 3-hydroxy-2-(3'-methylbut-2-enyl)-2-methyll-(N-isohexylamino) cyclopentane.

EXAMPLE 6 Following the procedure of Example 1, each of n-but-len-3-ol, n-pent-1-en-3-ol, 3-methylpent-l-en-3-ol and 3- ethylpent-1-en-3-ol is reacted with 2-methylcyclopentane- 1,3-dione to prepare 2-(n-but-2enyl)-2-methylcyclopentan-l,3-dione, 2-(n-pent-2-enyl)-2-methylcyclopentan-l,

3-dione, 2-(3-methylpent-2-enyl)-2-methylcyclopentan- 1,3-dione and 2-(3'-ethylpeut-2'-enyl)-2-methylcyclopentan-1,3-dione, respectively. Each of the thus-prepared diketo=icompounds is reduced following the procedure of Example 2 to prepare the respective 3-hydroxy compound,

3-hydroxy-2- (n-but-2'-enyl) -2-methylcyclopentanl-one, 3-hydroxy-2-(n-pent-2'-enyl) -2-methylcyclopentan-1- one, v

methyl n-butylamino) cyclopentane, 3-hydroxy-2- (3 -methylbut-2'-enyl) -2-methyl-1-(N,N-

methyl isopentylamino) cyclopentane, 3 -hydroxy-2-( 3 '-methylbut-2-enyl -2-methyl-1- (N,N- methyl isobutylamino') cyclopentane and 3vhydroxy-2-(3'-methylbut-2'-enyl) -2-methyl--l-(N,N-

" methyl isohexylamino) cyclopentane, respectively.

EXAMPLE 9 7 Following the pmiedur of Example thylma'gnesiiim bromide is reacted with 2-(ZV-methyIbut-Z' enyI) 2 methylcyclopentane-1,3-dione to yield 3-hydroxy-3 ethyl- 2-methyl-2-(3'-methylbut-2-enyl) cyclopentan 1 one which is reacted with methyl isohexylamine using the procedure of Example 5 to prepare 3-hydroxy-3-ethyl-2- methyl-2-(3-methylbut 2' enyl)-1-( l I,N-methylisohexylamino) cyclopentane. 7

EXAMPLE 10 Following the procedure of Example 3, l-vinyl-lhydroxycyclohexane is reacted with 2-methylcyclopentane-1,3 -dione to yield which is used as the starting material in the processes of Examples 2 and 7 or 9 to yield CH2 l ,53

a compound of Formula V is reacted with an amine, e.g., methyl isohexylamine, using the procedure of Example 5 to yield An excess of ammonia (about 10 ml.) is distilled into 30 ml. of anhydrous methanol, under nitrogen, and 283 mg. of sodium cyanoborohydride added. The mixture is adjusted to pH 5 by addition of dry halogen chloride and then 231 mg. of 3-hydroxy-2-allyl-2-methylcyclopentane-1- one is added. After about 48 hours, the mixture is poured into cold 5% sodium bicarbonate solution and then extnacted wit-h ether. The ethereal extract is washed, dried and evaporated under reduced pressure to yield 3-hydroxy- 2-allyl-2-methyl-l-aminocyclopentane.

6 What is claimed is: 1. A compound selected from those of the following formula:

R/\R1 R OH wherein, each of R, R R R and R is hydrogen or lower alkyl and R is methyl or ethyl.

2. A compound according to claim 1 wherein each of R and R is hydrogen, methyl or ethyl.

3. A compound according to claim 2 wherein R is hydrogen, methyl or ethyl.

4. A compound according to claim 3 wherein R is methyl.

5. A compound according to claim 4 wherein R is hydrogen or methyl and R is lower alkyl.

6. A compound according to claim 5 wherein R is isohexyl.

7. A compound according to claim 5 wherein R is methyl and R is isohexyl.

8. A compound according to claim 1 wherein R and R together form cyclopentyl or cyclohexyl.

9. A compound according to claim 8 wherein R is methyl, R is hydrogen, methyl or ethyl, R is hydrogen or methyl, and R is lower alkyl.

10. A compound according to claim 9 wherein R and R together form cyclohexyl.

11. A compound according to claim 10 wherein R is isohexyl.

- References Cited UNITED STATES PATENTS 2,390,597 '12/1945 Law et a1 260565 R LEWIS GOTTS, Primary Examiner D. R. PHILLIPS, Assistant Examiner US. Cl. X.R. 

